Mixed Dimetallic Cluster Fullerenes: ScGdO@C-3v(8)-C-82 and ScGdC2@C-2v(9)-C-82
Mixed Dimetallic Cluster Fullerenes: ScGdO@C-3v(8)-C-82 and ScGdC2@C-2v(9)-C-82
复制标题
混合双金属簇富勒烯：ScGdO@C-3v(8)-C-82 和 ScGdC2@C-2v(9)-C-82
DOI：
10.1021/acs.inorgchem.8b01646
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发表时间：
2018
影响因子：
4.6
通讯作者：
Chen Ning
中科院分区：
文献类型：
--
作者：
Yang Wei;Abella Laura;Wang Yaofeng;Li Xiaohong;Gu Jiali;Poblet Josep M.;Rodriguez-Fortea Antonio;Chen Ning
混合金属团簇富勒烯因其丰富的包裹团簇结构可变性，近年来得到了广泛的研究，在生物医学和分子电子器件等方面显示出巨大的应用潜力。然而，这一领域的研究大多集中在氮化物簇状富勒烯上，其他类型的混合金属簇状富勒烯目前还很少报道。在这里，我们报道了第一个混合金属氧化物簇富勒烯的合成和分离，ScGdO@C82，和一个新的混合双金属碳化物簇富勒烯，ScGdC2@C82。光谱和电化学研究结合密度泛函理论（DFT）计算，确定了两种簇状富勒烯（cf）的分子结构分别为ScGdO@C3v(8)-C82和ScGdC2@C2v(9)-C82。DFT计算还表明，这两种混合金属团簇可能存在于三个孤立的五边形规则(6)-C82、C3v(8)-C82和/或c2v (9)-C82cages中的任何一个中。电化学研究表明，ScGdO@C3v(8)- c82和ScGdC2@C2v(9)- c82的电化学间隙分别为1.49和1.08 V。此外，ScGdO@C3v(8)-C82与Sc2O@C3v(8)-C82、ScGdC2@C2v(9)-C82和Sc2C2@C2v(9)-C82的对比研究表明，尽管它们的结构非常相似，但用一个Gd离子取代一个Sc离子会导致它们的电化学行为和45sc核磁共振谱发生显著变化。
Mixed-metal cluster fullerenes have been extensively studied in recent years for their rich structural variability of the encaged clusters and have shown great potential in applied studies such as biomedicine and molecular electronic devices. However, the studies in this field have mostly concentrated on the nitride cluster fullerene, and very few other types of mixed-metal cluster fullerenes have been reported so far. Herein, we report the synthesis and isolation of the first mixed-metal oxide cluster fullerene, ScGdO@C82, and a novel mixed dimetallic carbide cluster fullerene, ScGdC2@C82. Spectroscopic and electrochemical studies combined with density functional theory (DFT) calculations assigned the molecular structure of the two cluster fullerenes (CFs) to ScGdO@C3v(8)-C82and ScGdC2@C2v(9)-C82, respectively. DFT calculations also suggested that these two mixed-metal clusters are likely to be found in any of the three isolated pentagon ruleCs(6)-C82,C3v(8)-C82and/orC2v(9)-C82cages. The electrochemical studies show that the electrochemical gap of ScGdO@C3v(8)-C82and ScGdC2@C2v(9)-C82are 1.49 and 1.08 V. Moreover, comparative studies of ScGdO@C3v(8)-C82and Sc2O@C3v(8)-C82, ScGdC2@C2v(9)-C82and Sc2C2@C2v(9)-C82showed that, despite their close structural resemblance, the replacement of one Sc ion by a Gd ion resulted in notable changes in their electrochemical behaviors as well as their45Sc NMR spectra.